U.S. patent number 6,660,691 [Application Number 10/164,107] was granted by the patent office on 2003-12-09 for herbicidal composition comprising benzoylpyrazoles and safener (isoxadifen or mefenpyr).
This patent grant is currently assigned to Aventis CropScience GmbH. Invention is credited to Hermann Bieringer, Erwin Hacker, Arnim Kohn, Andreas van Almsick, Lothar Willms, Hans-Joachim Zeiss, Frank Ziemer.
United States Patent |
6,660,691 |
Ziemer , et al. |
December 9, 2003 |
Herbicidal composition comprising benzoylpyrazoles and safener
(isoxadifen or mefenpyr)
Abstract
There are described herbicidal compositions comprising
herbicidal compounds of the formula I and a safener-active compound
of the formula II or III ##STR1## In formulae I, II and III, the
symbols R.sup.1 to R.sup.10 are hydrogen, halogen and various
organic radicals.
Inventors: |
Ziemer; Frank (Kriftel,
DE), van Almsick; Andreas (Karben, DE),
Kohn; Arnim (Wiesbaden, DE), Willms; Lothar
(Hofheim, DE), Zeiss; Hans-Joachim (Sulzbach/Ts.,
DE), Bieringer; Hermann (Eppstein, DE),
Hacker; Erwin (Hochheim, DE) |
Assignee: |
Aventis CropScience GmbH
(Frankfurt, DE)
|
Family
ID: |
7687298 |
Appl.
No.: |
10/164,107 |
Filed: |
June 4, 2002 |
Foreign Application Priority Data
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Jun 6, 2001 [DE] |
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10 127 328 |
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Current U.S.
Class: |
504/106;
504/271 |
Current CPC
Class: |
A01N
43/80 (20130101); A01N 43/80 (20130101); A01N
43/80 (20130101); A01N 43/56 (20130101); A01N
25/32 (20130101); A01N 43/80 (20130101); A01N
2300/00 (20130101) |
Current International
Class: |
A01N
43/72 (20060101); A01N 43/80 (20060101); A01N
025/32 (); A01N 043/80 () |
Field of
Search: |
;504/106,271,280 |
Foreign Patent Documents
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199 36 520 |
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Feb 2001 |
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DE |
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1 031 573 |
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Aug 2000 |
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EP |
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1 084 618 |
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Mar 2001 |
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EP |
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WO 99/58509 |
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Nov 1999 |
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WO |
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WO 99/66795 |
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Dec 1999 |
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WO |
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WO 01/17353 |
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Mar 2001 |
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WO |
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Other References
Database WPI AN 1999-313295, also referred to as XP
002215494..
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Primary Examiner: Clardy; S. Mark
Attorney, Agent or Firm: Frommer Lawernce & Haug LLP
Claims
We claim:
1. A herbicidal composition comprising A) a herbicidally active
amount of one or more compounds of the formula (I), ##STR5## in
which the symbols and indices have the following meanings: R.sup.1
is (C.sub.1 -C.sub.6)-alkyl; R.sup.2 is hydrogen or (C.sub.1
-C.sub.6)-alkyl; R.sup.3 is hydrogen, halogen, (C.sub.1
-C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-haloalkyl, (C.sub.1
-C.sub.6)-alkoxy, (C.sub.1 -C.sub.6)-haloalkoxy, (C.sub.1
-C.sub.6)-alkylthio, (C.sub.1 -C.sub.6)-alkylsulfinyl or (C.sub.1
-C.sub.6)-alkylsulfonyl; R.sup.4, R.sup.5, R.sup.6 are hydrogen or
(C.sub.1 -C.sub.6)-alkyl; R.sup.7 is (C.sub.1 -C.sub.6)-alkyl; a is
0, 1 or 2; and B) an antidote-effective amount of one or more
compounds of the formula (II) or (III) ##STR6##
in which R.sup.8, R.sup.9 and R.sup.10 independently of one another
are hydrogen or (C.sub.1 -C.sub.4)-alkyl, including the
stereoisomers and the salts conventionally used in agriculture.
2. A herbicidal composition as claimed in claim 1, wherein the
symbols and indices have the following meanings: R.sup.1 is
(C.sub.1 -C.sub.6)-alkyl; R.sup.2 is hydrogen or (C.sub.1
-C.sub.6)-alkyl; R.sup.3 is halogen or (C.sub.1 -C.sub.6)-alkyl;
R.sup.4, R.sup.5, R.sup.6 independently of one another are hydrogen
or (C.sub.1 -C.sub.6)-alkyl; R.sup.7 is (C.sub.1 -C.sub.6)-alkyl; a
is 0, 1 or 2.
3. A herbicidal composition as claimed in claim 1, wherein R.sup.8,
R.sup.9 and R.sup.10 in formula II and/or III independently of one
another are hydrogen or (C.sub.1 -C.sub.2)-alkyl.
4. A herbicidal composition as claimed in claim 1, wherein R.sup.3
in formula I is chlorine or methyl.
5. A herbicidal composition as claimed in claim 1, wherein a in
formula I is 2.
6. A herbicidal composition as claimed in claim 1, wherein the
weight ratio herbicide:safener amounts to 1:100 to 100:1.
7. A method of controlling harmful plants in crops, which comprises
applying a herbicidally active amount of a herbicide/safener
combination as claimed in claim 1 to the harmful plants, plants,
plant seeds or the area on which the plants grow.
8. A method as claimed in claim 7, wherein the plants are selected
from the group consisting of maize, wheat, rye, barley, oats, rice,
sorghum, cotton and soya.
9. A method as claimed in claim 7, wherein the plants are
genetically modified.
Description
The invention is in the technical field of the crop protection
products, in particular herbicide/antidote combinations (active
ingredient/safener combinations) which are suitable for use against
competing harmful plants in crops of useful plants.
A large number of herbicidal active ingredients are known as
inhibitors of the enzyme p-hydroxyphenylpyruvate dioxygenase
(HPPD). Only recently, more such active ingredients were disclosed
for example in WO 99/58509.
As is the case with many other herbicidal active ingredients, these
HPPD inhibitors too are not always sufficiently well tolerated by
(i.e. not sufficiently selective in) some important crop plants
such as maize, rice or cereals, so that their use is very limited.
They can therefore not be employed in some crops, or only at such
low application rates that the desired broad herbicidal activity
against harmful plants is not ensured. Specifically, many of the
abovementioned herbicides cannot be employed as fully selective
herbicides against harmful plants in maize, rice, cereals, sugar
cane and some other crops.
To overcome these disadvantages, it is known to employ herbicidal
active ingredients in combination with what is known as a safener
or antidote. Thus, for example, WO 99/66795 describes various
combinations of a large number of HPPD inhibitors with a
multiplicity of safeners.
A safener is understood as meaning a compound which compensates
for, or reduces, the phytotoxic properties of a herbicide with
regard to useful plants, without substantially reducing the
herbicidal activity against harmful plants.
Finding a safener for a specific groups of herbicides remains a
difficult task since the mechanisms by which a safener reduces the
harmful action of herbicides are not known in detail. The fact that
a compound in combination with a specific herbicide acts as safener
allows therefore no conclusions as to whether such a compound also
has a safener action with other groups of herbicides. Thus, it has
emerged when safeners were used for protecting the useful plants
from herbicide damage that the safeners may still exhibit certain
disadvantages in many cases. These include: the safener reduces the
activity of the herbicide against the harmful plants, the
useful-plant protecting properties are insufficient, the spectrum
of the useful plants in which the safener/herbicide is to be
employed is not sufficiently wide in combination with a given
herbicide, a given safener cannot be combined with a sufficiently
large number of herbicides.
It was an object of the present invention to provide further
combinations of herbicides from the group of the HPPD inhibitors
with safeners which are suitable for increasing the selectivity of
these herbicides with regard to important crop plants.
There have now been found novel combinations of specific herbicides
from the group of the HPPD inhibitors, specifically from the group
of the benzoylpyrazoles, which have selected substituents attached
in the 3-position of the benzoyl moiety, with some selected
safeners which increase the selectivity of these herbicides with
regard to important crop plants.
The invention therefore relates to a herbicidally active
composition comprising A) a herbicidally active amount of one or
more compounds of the formula (I), ##STR2##
in which the symbols and indices have the following meanings:
R.sup.1 is (C.sub.1 -C.sub.6)-alkyl; R.sup.2 is hydrogen or
(C.sub.1 -C.sub.6)-alkyl; R.sup.3 is hydrogen, halogen, (C.sub.1
-C.sub.6)-alkyl, (C.sub.1 -C.sub.6)-haloalkyl, (C.sub.1
-C.sub.6)-alkoxy, (C.sub.1 -C.sub.6)-haloalkoxy, (C.sub.1
-C.sub.6)-alkylthio, (C.sub.1 -C.sub.6)-alkylsulfinyl or (C.sub.1
-C.sub.6)-alkylsulfonyl; R.sup.4, R.sup.5, R.sup.6 are hydrogen or
(C.sub.1 -C.sub.6)-alkyl; R.sup.7 is (C.sub.1 -C.sub.6)-alkyl; a is
0, 1 or 2; and B) an antidote-effective amount of one or more
compounds of the formula (II) or ##STR3##
in which the symbols have the following meanings: R.sup.8, R.sup.9,
R.sup.10 independently of one another are hydrogen or (C.sub.1
-C.sub.4)-alkyl, including the stereoisomers and the salts
conventionally used in agriculture.
Herbicidally active amount for the purposes of the invention refers
to an amount of one or more herbicides suitable for having an
adverse effect on plant growth.
Antidote-effective amount for the purposes of the invention refers
to an amount of one or more safeners suitable for at least
partially counteracting the phytotoxic effect of the herbicide or
herbicide mixture on a useful plant.
Unless specifically otherwise defined, the definitions given
hereinbelow generally apply to the radicals in the formulae of (I)
to (III) and the subsequent formulae.
The radicals alkyl, alkoxy, haloalkyl, haloalkoxy and alkylthio and
the corresponding unsaturated and/or substituted radicals in the
carbon skeleton can be in each case straight-chain or branched.
Alkyl radicals, also in the composite meanings such as alkoxy,
haloalkyl and the like, preferably have 1 to 4 carbon atoms and
are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or
2-butyl. "(C.sub.1 -C.sub.4)-alkyl" is the abbreviation for alkyl
having 1 to 4 carbon atoms; the same applies analogously to other
general definitions of radicals with bracketed ranges of the
possible number of carbon atoms.
Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl is
alkyl, alkenyl or alkynyl which is partially or fully substituted
by halogen, preferably by fluorine, chlorine, and/or bromine, in
particular by fluorine or chlorine, for example CF.sub.3,
CHF.sub.2, CH.sub.2 F, CF.sub.2 CF.sub.3, CH.sub.2 FCClFH,
CCl.sub.3, CHCl.sub.2, CH.sub.2 CH.sub.2 Cl. Haloalkoxy is, for
example, OCF.sub.3, OCHF.sub.2, OCH.sub.2 F, OCF.sub.2 CF.sub.3,
OCH.sub.2 CF.sub.3 and OCH.sub.2 CH.sub.2 Cl. The same applies
analogously to other halogen-substituted radicals.
Formulae (I) to (III) also encompass all stereoisomers which have
the same topological linkage of the atoms, and their mixtures. Such
compounds contain one or more asymmetric carbon atoms or else
double bonds which are not specified individually in the general
formula. The possible stereoisomers which are defined by their
specific spatial shape such as enantiomers, diasteriomers, Z- and
E-isomers can be obtained from stereoisomer mixtures by customary
methods or else be prepared by stereoselective reactions in
combination with the use of stereochemically pure starting
materials.
Suitable herbicidal active ingredients are in accordance with the
invention those compounds of the formula (I) which cannot be
employed on their own, or which can not be employed optimally on
their own, in crops of useful plants such as cereal crops, rice or
maize since they cause too much damage to the crop plants.
Herbicides of the formula (I) are disclosed for example in WO
99/65314 and WO 99/58509.
The publications cited contain detailed information on preparation
processes and starting materials. These publications are expressly
referred to, they are incorporated into the present application by
reference.
The compounds of the formula (II) are known for example from WO
91/07874 and the literature cited therein and can be prepared by,
or analogously to, the methods described therein. The compounds of
the formula (III) are known from WO 95/07897 and literature cited
therein and can be prepared by, or analogously to, the methods
described therein.
The publications cited contain detailed information on preparation
processes and starting materials. These publications are expressly
referred to, they are incorporated into the present application by
reference.
For the purposes of the present application, the term "herbicidal
compositions" and "herbicide/safener combinations" are to be
considered as equal.
Preferred herbicidal compositions are those which comprise
compounds of the formula (I), in which the symbols and indices have
the following meanings: R.sup.1 is (C.sub.1 -C.sub.6)-alkyl;
R.sup.2 is hydrogen or (C.sub.1 -C.sub.6)-alkyl; R.sup.3 is halogen
or (C.sub.1 -C.sub.6)-alkyl; R.sup.4, R.sup.5, R.sup.6 are
hydrogen, (C.sub.1 -C.sub.6)-alkyl; R.sup.7 is (C.sub.1
-C.sub.6)-alkyl; a is 0, 1 or 2.
Also preferred are herbicidal compositions comprising safeners of
the formula (II) and/or (III), in which R.sup.8, R.sup.9 and
R.sup.10 independently of one another are hydrogen or (C.sub.1
-C.sub.2)-alkyl.
Especially preferred are herbicidal compositions comprising
compounds of the formula (I), in which R.sup.3 is chlorine or
methyl.
Also especially preferred are herbicidal compositions comprising
compounds of the formula (I) in which a is 2.
The compounds mentioned herein as safeners (antidotes) reduce or
compensate for phytotoxic effects which may occur when using the
herbicidal active ingredients of the formula (I) in crops of useful
plants without essentially adversely affecting the efficacy of the
herbicidal active ingredients against harmful plants. Thus, the
field of application of conventional crop protection agents can be
widened considerably and extended to, for example, crops such as
wheat, barley, rice and maize in which the use of the herbicides
has previously not been possible or only with limitations, that is
to say at low dosages with a narrow spectrum of action.
Herbicidal active ingredients and the safeners mentioned can be
applied together (as readymix or by the tank mix method) or
sequentially in any desired sequence. The weight ratio of safener
to herbicidal active ingredient may vary within wide limits and is
preferably in the range of from 1:100 to 100:1, in particular from
1:10 to 10:1. The optimum amount of herbicidal active ingredient
and safener depend in each case on the type of the herbicidal
active ingredient used or on the safener used and on the nature of
the plant stock to be treated and can be determined in each
individual case by simple routine preliminary experiments.
Main fields of application for the use of the combinations
according to the invention are especially maize and cereal crops
such as, for example, wheat, rye, barley, oats, rice, sorghum, but
also cotton and soybean, preferably cereals, rice and maize.
Depending on their properties, the safeners employed in accordance
with the invention may be used for pretreating the seed of the crop
plant (seed dressing) or introduced into the seed furrows prior to
sowing or used together with the herbicide before or after
emergence of the plants. Pre-emergence treatment includes not only
the treatment of the area under cultivation before sowing, but also
the treatment of the sown soil which does not yet sustain
vegetation. Preferred is the application together with the
herbicide. Tank mixes or ready mixes may be employed for this
purpose.
The safener application rates required may vary within wide limits,
depending on the indication and the herbicidal active ingredient
used; they are, as a rule, in the range of from 0.001 to 5 kg,
preferably from 0.005 to 0.5 kg, of active ingredient per
hectare.
The present invention therefore also relates to a method of
protecting crop plants from phytotoxic side effects of herbicides
of the formula (I), which comprises applying an antidote-effective
amount of a compound of the formula (II) and/or (III) before, after
or simultaneously with the herbicidal active ingredient A of the
formula (I) to the plants, plant seeds or the area under
cultivation.
The herbicide/safener combination according to the invention may
also be employed for controlling harmful plants in crops of known
genetically modified plants or genetically modified plants yet to
be developed. As a rule, the transgenic plants are distinguished by
particularly advantageous properties, for example by resistances to
certain crop protection agents, resistances to plant diseases or to
causative agents of plant diseases such as specific insects or
microorganisms such as fungi, bacteria or viruses. Other particular
properties concern for example the harvested crop with regard to
quantity, quality, storability, composition and specific
constituents. Thus, transgenic plants are known with an increased
starch content or a modified starch quality, or those with a
different fatty acid composition of the harvested crop.
Preferred is the use of the combinations according to the invention
in economically important transgenic crops of useful plants and
ornamentals, for example of cereals such as wheat, barley, rye,
oats, sorghum and millet, rice, cassaya and maize, or else crops of
sugar beet, cotton, soybean, oilseed rape, potato, tomato, pea and
other vegetables.
When the combinations according to the invention are used in
transgenic crops, effects in addition to the effects to be observed
against harmful plants in other crops are frequently found, which
are specific for application in the particular transgenic crop, for
example a modified or specifically widened weed spectrum which can
be controlled, modified application rates which may be employed for
the application, preferably good combinability with the herbicides
to which the transgenic crop is resistant, and an effect on growth
and yield of the transgenic crop plants.
The invention thus also relates to the use of the combination
according to the invention for controlling harmful plants in
transgenic crop plants.
The safeners of the formulae (II) and (III) and their combinations
with one or more of the abovementioned herbicidal active
ingredients of the formula (I) can be formulated in various ways,
depending on the prevailing biological and/or chemico-physical
parameters. Suitable possibilities of formulation are, for example,
wettable powders (WP), emulsifiable concentrates (EC),
water-soluble powders (SP), water-soluble concentrates (SL),
concentrated emulsions (BW) such as oil-in-water and water-in-oil
emulsions, sprayable solutions or emulsions, capsule suspensions
(CS), oil- or water-based dispersions (SC), suspoemulsions,
suspension concentrates, dust (DP), oil-miscible solutions (OL),
seed-dressing products, granules (GR) in the form of microgranules,
spray granules, coated granules and absorption granules, granules
for soil application or broadcasting, water-soluble granules (SG),
water-dispersible granules (WG), ULV formulations, microcapsules
and waxes.
These individual formulation types are known in principle and are
described, for example, in: Winnacker-Kuchler, "Chemische
Technologie" [Chemical engineering], Volume 7, C. Hauser Verlag
Munich, 4th Ed., 1986; Wade van Valkenburg, "Pesticide
Formulations", Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying
Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries which may be required, such as inert
materials, surfactants, solvents and further additives are likewise
known and described, for example, in: "Handbook of Insecticide Dust
Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N. J., H.
v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J.
Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed.,
Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers
Annual", MC PubI. Corp., Ridgewood N.J.; Sisley and Wood,
"Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y.
1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte"
[Surface-active ethylene oxide adducts], Wiss. Verlagsgesell.,
Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie", Volume
7, C. Hauser Verlag Munich, 4th Ed. 1986.
Based on these formulations, combinations with other crop
protectants such as insecticides, acaricides, herbicides,
fungicides, and with safeners, fertilizers and/or growth regulators
may also be prepared, for example in the form of a readymix or a
tank mix.
Wettable powders are preparations which are uniformly dispersible
in water and which, besides the active ingredient, additionally
comprise ionic and/or nonionic surfactants (wetters, dispersants),
for example polyoxethylated alkylphenols, polyoxethylated fatty
alcohols, polyoxethylated fatty amides, fatty alcohol polyglycol
ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium
lignosulfonates, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate,
sodium dibutylnaphthalene-sulfonate, or else sodium
oleoylmethyltaurinate, in addition to a diluent or inert substance.
To prepare the wettable powders, the herbicidal active ingredients
are ground finely, for example in customary apparatuses such as
hammer mills, blower mills and air-jet mills, and simultaneously or
subsequently mixed with the formulation auxiliaries.
Emulsifiable concentrates are prepared for example by dissolving
the active ingredient in an organic solvent, for example butanol,
cyclohexanone, DMF or else high-boiling hydrocarbons such as
saturated or unsaturated aliphatic or alicyclic substances,
aromatic substances or mixtures of these organic solvents with
addition of one or more ionic and/or nonionic surfactants
(emulsifiers). The following are examples of emulsifiers which may
be used: calcium alkylarylsulfonates such as calcium
dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid
polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol
polyglycol ethers, propylene oxide/ethylene oxide condensates,
alkyl polyethers, sorbitan esters such as, for example, sorbitan
fatty acid esters or polyoxyethylene sorbitan esters such as
polyoxyethylene sorbitan fatty acid esters. Dusts are obtained in
general by grinding the active ingredients with finely divided
solid materials, for example talc, natural clays such as kaolin,
bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates may be water- or oil-based. They can be
prepared for example by wet-milling by means of commercially
available beat mills, if appropriate with addition of surfactants
as, for example, have already been listed above in the case of the
other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be prepared
for example by means of stirrers, colloid mills and/or static
mixers using aqueous organic solvents and, if appropriate,
surfactants as, for example, have already been listed above in the
case of the other formulation types.
Granules can be produced either by spraying the active ingredient
onto absorptive granulated inert material or by applying active
ingredient concentrates to the surface of carriers such as sand,
kaolinite or of granulated inert material by means of binders, for
example polyvinyl alcohol, sodium polyacrylate or else mineral
oils. Suitable active ingredients may also be granulated in the
manner which is conventional for the production of fertilizer
granules, if desired as a mixture with fertilizers.
As a rule, water-dispersible granules are prepared by the customary
method such as spray-drying, fluidized-bed granulation, disk
granulation, mixing by means of high-speed mixers, and extrusion
without solid inert material.
To prepare disk, fluidized-bed, extruder and spray granules, see,
for example, methods in "Spray-Drying Handbook" 3rd ed. 1979, G.
Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and
Engineering 1967, pages 147 et seq.; "Perry's Chemical Engineer's
Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
For further details on the formulation of crop protection agents
see, for example, G. C. Klingman, "Weed Control as a Science", John
Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer,
S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific
Publications, Oxford, 1968, pages 101-103.
As a rule, the agrochemical preparations comprise from 0.1 to 99%
by weight, in particular from 0.1 to 95% by weight, of active
ingredients of the formula (II) and/or (III) or of the
herbicide/antidote active ingredient mixture (I) and (II)/(III) and
from 1 to 99.9% by weight, in particular from 5 to 99.8% by weight,
of a solid or liquid additive and from 0 to 25% by weight, in
particular from 0.1 to 25% by weight, of a surfactant.
In wettable powders, the active ingredient concentration is, for
example, from approximately 10 to 90% by weight, the remainder to
100% by weight being composed of customary formulation components.
In the case of emulsifiable concentrates, the concentration amounts
to approximately 1 to 80% by weight. Formulations in the form of
dusts comprise from approximately 1 to 20% by weight of active
ingredients, sprayable solutions from approximately 0.2 to 20% by
weight of active ingredients. In the case of granules such as
water-dispersible granules, the active ingredient content depends
partly on whether the active compound is in liquid or solid form.
As a rule, the active compound content in the water-dispersible
granules is between 10 and 90% by weight.
In addition, the active ingredient formulations mentioned comprise,
if appropriate, the adhesives, wetters, dispersants, emulsifiers,
penetrants, preservatives, antifreeze agents, solvents, fillers,
carriers, colorants, antifoams, evaporation inhibitors, pH
regulators and viscosity regulators which are conventional in each
case.
The necessary application rates of the herbicides of the formula
(I) varies with the external conditions such as, inter alia,
temperature, humidity and the type of the herbicide used. It can be
varied within wide limits, for example between 0.001 and 10.0 kg/ha
or more of active substance, but it is preferably between 0.005 and
kg/ha.
The examples which follow illustrate the invention:
A. FORMULATION EXAMPLES a) A dust is obtained by mixing 10 parts by
weight of a compound of the formula (II) and/or (III) or of an
active ingredient mixture of a herbicidal active ingredient of the
formula (I) and a safener of the formula (II) and/or (III) and 90
parts by weight of talc as inert substance and comminuting the
mixture in a hammer mill. b) A wettable powder with is readily
dispersible in water is obtained by mixing 25 parts by weight of a
compound of the formula (II) and/or (III) or of an active
ingredient mixture of a herbicidal active ingredient of the formula
(I) and a safener of the formula (II) and/or (III), 64 parts by
weight of kaolin-containing quartz as inert material, 10 parts by
weight of potassium lignosulfonate and 1 part by weight of sodium
oleoylmethyltaurinate as wetter and dispersant and grinding the
mixture in a pinned-disk mill. c) A dispersion concentrate which is
readily dispersible in water is obtained by mixing 20 parts by
weight of a compound of the formula (II) and/or (III) or of an
active ingredient mixture of a herbicidal active ingredient of the
formula (I) and a safener of the formula (II) and/or (III), 6 parts
by weight of alkylphenol polyglycol ether (.RTM.Triton X 207), 3
parts by weight of isotridecanol polyglycol ether (8 EO) and 71
parts by weight of paraffinic mineral oil (boiling range for
example approx. 255 to above 277.degree. C.) and grinding the
mixture in a bowl mill to a fineness of below 5 microns. d) An
emulsifiable concentrate is obtained from 15 parts by weight of a
compound of the formula (II) and/or (III) or of an active
ingredient mixture of a herbicidal active ingredient of the formula
(I) and a safener of the formula (II) and/or (III), 75 parts by
weight of cyclohexanone as solvent and 10 parts by weight of
oxethylated nonylphenol as emulsifier. e) Water-dispersible
granules are obtained by mixing
75 parts by weight of a compound of the formula (II) and/or (III)
or of an active ingredient mixture of a herbicidal active
ingredient of the formula (I) and a safener of the formula (II)
and/or (III), 10 parts by weight of calcium lignosulfonate, 5 parts
by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl
alcohol and 7 parts by weight of kaolin,
grinding the mixture on a pinned-disk mill and granulating the
powder in a fluidized bed by spraying on water as granulation
liquid. f) Water-dispersable granules are also obtained by
homogenizing and precomminuting
25 parts by weight of a compound of the formula (II) and/or (III)
or of an active ingredient mixture of a herbicidal active
ingredient of the formula (I) and a safener of the formula (II)
and/or (III), 5 parts by weight of sodium
2,2'-dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of
sodium oleoylmethyltaurinate, 1 parts by weight of polyvinyl
alcohol, 17 parts by weight of calcium carbonate and 50 parts by
weight of water
in a colloid mill, subsequently milling the mixture in a beat mill
and atomizing and drying the resulting suspension in a spray tower
by means of a single-substance nozzle.
B BIOLOGICAL EXAMPLES
In the experiments which follow, compositions according to the
invention comprising safeners S1, S2 and herbicides H1 and H2 were
employed. ##STR4##
Post-Emergence Experiments:
Seeds of useful plants are placed in soil in the open and covered
with soil. At the two-leaf stage, the plants are treated with the
herbicides formulated as emulsifiable concentrates or dust and, for
comparison purposes, with herbicides and safeners in the form of
aqueous dispersions or suspensions or emulsions at an application
rate of 300 to 800 l of water per ha (converted) at various
dosages. The damage to the useful plants was scored visually 14 or
21 days after the treatment. The results of Examples B1 to B4
demonstrate that the damage in the useful plants was reduced
considerably by using the herbicidal compositions comprising
herbicide and safener in comparison with using the herbicide only.
Depending on the rate of application, the species of the useful
plant and the type of the composition according to the invention,
the damage is reduced by up to 100% in comparison with using the
herbicide. The dosage is shown in grams of active substance per
hectare (g a.i/ha).
Example B1, Reduction of damage in maize, 14 days post-treatment
Dosage [g a.i/ha] Dosage [g a.i/ha] Safener S1 Herbicide H1 Damage
reduction 50 50 -100% Example B2, Reduction of damage in wheat, 14
days post-treatment Dosage [g a.i/ha] Dosage [g a.i/ha] Safener S2
Herbicide H1 Damage reduction 150 150 -57% Example B3, Reduction of
damage in maize, 21 days post-treatment Dosage [g a.i/ha] Dosage [g
a.i/ha] Safener S1 Herbicide H1 Damage reduction 150 150 -93%
Example B4, Reduction of damage in maize, 21 days post-treatment
Dosage [g a.i/ha] Dosage [g a.i/ha] Safener S1 Herbicide H2 Damage
reduction 150 150 -92%
* * * * *